CN106602004A - High-safety power lithium ion secondary battery composite positive material and preparation method thereof - Google Patents
High-safety power lithium ion secondary battery composite positive material and preparation method thereof Download PDFInfo
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- CN106602004A CN106602004A CN201510674356.8A CN201510674356A CN106602004A CN 106602004 A CN106602004 A CN 106602004A CN 201510674356 A CN201510674356 A CN 201510674356A CN 106602004 A CN106602004 A CN 106602004A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a high-safety power lithium ion secondary battery composite positive material and a preparation method thereof, the chemical formula of the high-safety power lithium ion secondary battery composite positive material is LixNiyCozMn1-y-zO2, 0.9 < x < 1.3, 0 <y< 1, 0 < z< 1, y+ z< =1, tapping density is greater than or equal to 1.5g /cm<3>, the preparation method is as follows: first, sodium hydroxide/potassium hydroxide mixed with ammonia is added into a solution of a soluble salt containing Ni-Co-Mn elements to obtain a Ni-Co-Mn hydroxide precursor, the dried precursor is mixed evenly with a lithium source or lithium hydroxide or lithium carbonate for high temperature sintering to obtain the LixNiyCozMn1-y-zO2, the LixNiyCozMn1-y-zO2 is added into a well-dissolved aluminum solution for drying by vacuum drying and heat treatment at 400-700 DEG C to obtain Al-coated LixNiyCozMn1-y-zO2. The coated positive electrode material has good safety performance and circulation performances, and can be used for long circulation and high safety lithium ion power batteries.
Description
Technical field
The present invention relates to a kind of lithium ion secondary battery anode material and preparation method thereof, especially relates to
And a kind of power lithium-ion rechargeable battery composite positive pole and preparation method thereof.
Background technology
State Council is printed and distributed in energy-conservation and new-energy automobile industrial development planning (2012-2020)
Point out, new-energy automobile, can effectively alleviate the energy and ambient pressure, reduce automobile fuel consumption
Amount, alleviates fuel oil disparities between supply and demand, reduces exhaust emissions, improves atmospheric environment.New-energy automobile
Refer to and adopt Novel power system, the automobile for entirely or primarily driving by novel energy, mainly
Including pure electric automobile, plug-in hybrid-power automobile and fuel cell car.In planning clearly
Propose that main task, to strengthen new-energy automobile key core technical research, carries forward vigorously power current
Pool technology is innovated, study emphasis electrokinetic cell system safety, and reliability consideration and lightweight set
Meter, accelerate to develop electrokinetic cell both positive and negative polarity, barrier film, the critical material such as electrolyte and its production,
The equipment such as control and detection, is disposed in advance on the great basis of electrokinetic cell and cutting edge technology field,
The research such as study emphasis high specific energy power battery material, new system and new construction, new technology.
Its main target is：By 2015, it is pure it is electronic into without car max. speed be not less than 100 kilometers/
Hour, under pure electric drive mode comprehensive operating mode driving course it is not low with 150 kilometers and 50 kilometers；
Power battery module specific energy reach 150 watt-hours/kilogram more than, cost be down to 2 yuan/watt-hour with
Under, service life cycle is stably reached 2000 times or more than 10 years, and electric propulsion system power is close
Degree reaches 2.5 kilowatts/kilogram, and cost is down to below 200 yuan/kilowatt.To the year two thousand twenty, power
Battery module specific energy reach 300 watt-hours/kilogram, cost is down to below 1.5 yuan/watt-hour.
According to the target that State Council is proposed to power battery module specific energy and cycle life, extremely
Power battery module in 2015 reach 150 watt-hours/kilogram more than, be converted to cell, its
Energy density take around reach 170-190 watt-hours/kilogram, to the year two thousand twenty, electrokinetic cell mould
Block specific energy reach 300 watt-hours/kilogram, its corresponding cell energy density is at least 330
Watt-hour/kilogram more than, cycle life is stably reached 2000 times or more than 10 years, to energy and
Cycle life proposes very high requirement.
The positive electrode of industrialization at present mainly has cobalt acid lithium, LiFePO 4, LiMn2O4
And ternary material, wherein cobalt acid lithium is still the maximum positive electrode of current consumption, but due to cobalt valency
Lattice are expensive, and relatively costly, new substitution material is actively being found by battery material manufacturer.
Li-Ni class multi-element composite positive pole materials are the lithium battery anodes of nickel cobalt additive Mn and coating modification
Material, its performance are better than one-component positive electrode, there is obvious nickel cobalt manganese cooperative effect,
Wherein cobalt energy stabilizing material structure, improve material conductivity and suppress cation mixing, can improve
Positive electrode cyclical stability；Nickel is main electro-chemical activity element, it is possible to provide very high can
Inverse capacity；Manganese can improve material safety performance, while reducing production cost.It is many in Li-Ni classes
In first composite positive pole, most representativeness has LiNi1/3Co1/3Mn1/3O2,
LiNi0.5Co0.2Mn0.3O2, LiNi0.6Co0.2Mn0.2O2, structure is α-NaFeO2Type stratiform
Structure, belongs to trigonal system, R-3m space groups.
At present, in response to country's call, Li-Ni base composite positive poles are made to be applied to power
On battery and new-energy automobile Vehicular battery, but the crystallization-stable of Li-Ni base composite positive poles
Property is relatively low, and its cycle performance and thermal stability also need further to improve.
The content of the invention
The purpose of the present invention be for existing Li-Ni bases composite positive pole in charge and discharge cycles
There is side reaction with electrolyte, a kind of problem for causing cycle performance of battery to decline, there is provided Li-Ni
The synthetic method of base composite positive pole, is carried out uniformly to body phase material using wet method cladding process
Cladding, makes clad play one's part to the full, and suppresses corrosion of the electrolyte to material, prevents cladding
Uneven, portion of material is exposed in the electrolytic solution, the phenomenon for causing battery performance to decline, and meets
Lithium battery power market field high safety and macrocyclic needs.
In order to achieve the above object, the present invention has following technical scheme：
A kind of power lithium-ion rechargeable battery composite positive pole of high safety of the present invention, chemistry
Formula is LixNiyCozMn1-y-zO2, 0.9<x<1.3,0<y<1,0<z<1, y+z≤1；It is described
Power lithium-ion rechargeable battery composite positive pole be powder, tap density >=1.5g/cm3。
The system of the power lithium-ion rechargeable battery composite positive pole of high safety of the present invention
Preparation Method is as follows：
First, structural formula is produced for NiyCozMn1-y-z(OH)2Granular precursor, washing,
It is dried；Then mix homogeneously with lithium carbonate, lithium nitrate or Lithium hydrate, enter in being put into high temperature furnace
Row sintering, broken, crushing, screening；The material of sintering crushing is added to the silicon source solution for preparing
In, vacuum drying is uniformly coated the Li-Ni based composite oxides of Al by sintering
Grain.Concrete steps include：
(1)NiyCozMn1-y-z(OH)2Preparation：
By soluble nickel salt, cobalt salt and manganese salt according to Ni:Co:Mn=y:z:(1-y-z) rub
, than being made into mixed solution A, the concentration of mixed solution is 0.1～3mol/L for you, and compound concentration is
NaOH solution B of 0.4～10mol/L, concentration are the ammonia spirit C of 2～10mol/L；
Pure water is added in reaction vessel, pH to 9.5～12 is adjusted with NaOH solution and ammonia, by A,
Tri- kinds of solution of B, C are added in reaction vessel simultaneously, and reaction temperature is maintained at 50～80 DEG C,
PH is maintained at 9.5～12, and mixing speed 200-800r/min, the whole process of reaction lead to inertia
Gas shield；The precipitation for obtaining is filtered after terminating by reaction, washing, is dried at 80-200 DEG C
4-8h obtains NiyCozMn1-y-z(OH)2；
(2)LixNiyCozMn1-y-zO2Preparation：
Step (1) is obtained into NiyCozMn1-y-z(OH)2With lithium source Li in molar ratio：M
(M=NiyCozMn1-y-z(OH)2) mixed equal to 0.9～1.2；By the material of mix homogeneously
Material is sintered in high temperature furnace, and sintering temperature is 700-1100 DEG C, and sintering time is 10～16h,
Then cooling, it is broken, crush, screening, except ferrum, obtain LixNiyCozMn1-y-zO2Material；
(3) liquid phase coating aluminum
Step (2) resulting materials LixNiyCozMn1-y-zO2It is added to the solubility for having dissolved
Feed liquid is obtained in the solution of silicon source, feed temperature is 30～70 DEG C, and solid content is 10～50%,
Gained feed liquid is stirred, is vacuum dried, is then obtained in 400～800 DEG C of 5～10h of constant temperature
To the Li being evenly coatedxNiyCozMn1-y-zO2Material.
The nickel salt, cobalt salt and manganese salt, using sulfate, chlorate, nitrate, acetate
In one or more.
The lithium source is using one or more in lithium carbonate, Lithium hydrate, lithium nitrate.
Source of aluminium, using aluminum isopropylate., aluminum oxyhydroxide, aluminum nitrate, aluminum chloride, nanometer
One or more in alumina fluid dispersion, the covering amount of aluminum is in 0.03～5wt%.
Preferably, when being stirred to gained feed liquid in step (3), mixing speed be 100～
1000r/min, mixing time are 0.5～4h.
Due to taking above technical scheme, it is an advantage of the current invention that：
(1) Li-Ni base composite positive poles of the invention, it is equal due to existing in particle surface
Even clad, can suppress Li-Ni bases composite positive pole and electrolyte in charge and discharge process
Reaction, prevent due to coat it is uneven, cause portion of material exposed, cause under battery performance
The phenomenon of drop, so as to lift battery security and cyclicity；
(2) Li-Ni composite positive poles of the invention are coated obtained from Al by wet method,
Aluminum can be made to keep good being evenly coated property in the process of drying using vacuum drying during preparation,
Li in positive electrode can also be avoided+Excessive abjection, affect the electrifications such as capacity and the circulation of material
Performance is learned, by using the Li-Ni composite positive poles of the present invention, discharge capacity can be obtained
Greatly, the safety especially good rechargeable nonaqueous electrolytic battery of cycle performance.
Description of the drawings
Fig. 1 is the LiNi prepared in embodiment 10.6Co0.2Mn0.2O2XRD spectrum；
Before and after Fig. 2 is the Li-Ni based composite oxide Surface coating Al obtained in embodiment 1
Scanning electron microscope (SEM) photograph (left figure for cladding before, right figure for cladding after)；
Fig. 3 is the Li-Ni based composite oxide granular powders of the Al claddings obtained in embodiment 1
The cycle performance figure of the made soft-package battery in end.
Specific embodiment
By the following examples the detailed process of the present invention is described further, there is provided these realities
Example is applied only for the explanation present invention, the scope that should not be understood to limit the present and master
Purport.
Referring to Fig. 1-Fig. 3 and table 1：
Embodiment 1
Nickel sulfate, cobaltous sulfate and manganese sulfate are made into into mixed solution according to Ni：Co：Mn mole
Than for 0.6:0.2:0.2 mix homogeneously, the total mole number of tri- kinds of transition metal ionss of Ni, Co, Mn
For 2mol/L, then by the NaOH solution and transition metal ion solution and 4mol/L of 4mol/L
Ammonia be simultaneously added in reaction vessel, the pH value for control reaction system is 11.5, and reaction is warm
Spend for 60 DEG C.Then, after the precipitation for obtaining filtration, washing, it is dried 12 hours at 120 DEG C.
By lithium carbonate and Ni0.6Co0.2Mn0.2(OH)2According to Li/M=1.12, (M is
Ni0.6Co0.2Mn0.2(OH)2) ratio mixed, in high-speed mixer mix homogeneously,
900 DEG C of calcining 12h in Muffle furnace, air of the atmosphere for 3L/min, material furnace cooling are crushed
400 mesh sieves are crossed afterwards.30mL deionized waters are added in agitator tank, adds 0.07g aluminum isopropylate. to stir
Mix dissolving, after 50 DEG C of constant temperature 30min, add 30g is above-mentioned sieve after material, 50 DEG C of constant temperature 3h,
Dried with double-cone vacuum dryer afterwards, the material after drying is put in high temperature furnace, 500 DEG C
300 mesh sieves are crossed after sintering 4h, it is 0.03% to be evenly coated to finally give Al covering amounts
LiNi0.6Co0.2Mn0.2O2.The scanning electron microscope (SEM) photograph and XRD figure of material is as shown in Figure 1 and Figure 2.Knot
Fruit shows gained LiNi0.6Co0.2Mn0.2O2For pure phase, with preferable degree of crystallinity.Fig. 2 is scanned
Electronic Speculum right figure shows that material has the clad of the Al being substantially evenly coated.
By the LiNi of above-mentioned synthesis0.6Co0.2Mn0.2O2Positive electrode, acetylene black, KS-6, PVDF
According to the ratio mix homogeneously that mass ratio is 9.2 ︰, 0.3 ︰, 0.2 ︰ 0.3, appropriate NMP is added,
Uniform slurry is made in stirring；Slurry is uniformly applied on aluminium foil, air dry oven is put into
After drying, place into 120 DEG C of vacuum drying oven and be vacuum dried 12 hours；With punching after natural cooling
Piece machine goes out the disk of a diameter of 16mm, and disk is placed on tablet machine the pressure with 10MPa
Positive plate is obtained after compacting.With homemade positive plate as positive pole, lithium piece is negative pole,
Celgard2400 microporous polypropylene membranes be barrier film, the LiPF of 1mol/L6/EC+DMC(v:V=1:1)
For electrolyte, in water content and oxygen content all in the glove box full of argon of below 0.1ppm
CR2016 type experimental cells are assembled into, are entered in 2.75～4.25V voltage ranges with the multiplying power of 0.1C
Row charge-discharge test, discharge capacity reaches 174mAh/g to material first, and Soft Roll circulates 1800 appearances
Amount conservation rate is 94%, and the circulation figure of material is as shown in Figure 3.
Embodiment 2-6
Based on pure phase LiNi that embodiment 1 is obtained0.6Co0.2Mn0.2O2, add the different of different quality
Aluminum tripropoxide, makes the covering amount of final aluminum be respectively 0.1%, 0.5%, 1%, 3%, 5%, its
His step is with embodiment 1.
Embodiment 7-9
The Li-Ni class composite positive poles of the oxide cladding of Al are prepared similar to embodiment 1,
Except, after Al claddings are carried out, sintering temperature is respectively 400 DEG C, 600 DEG C, 700 DEG C.
Embodiment 10
Nickel sulfate, cobaltous sulfate and manganese sulfate are made into into mixed solution according to Ni：Co：Mn mole
Than for 0.5:0.2:0.3 mix homogeneously, the total mole number of tri- kinds of transition metal ionss of Ni, Co, Mn
For 1mol/L, then by the NaOH solution and transition metal ion solution and 2mol/L of 2mol/L
Ammonia be simultaneously added in reaction vessel, the pH value for control reaction system is 11.4, and reaction is warm
Spend for 60 DEG C.Then, after the precipitation for obtaining filtration, washing, it is dried 12 hours at 120 DEG C.
By lithium carbonate and Ni0.5Co0.2Mn0.3(OH)2According to Li/M=1.1 (M=
Ni0.5Co0.2Mn0.3(OH)2) ratio mixed, the mix homogeneously in inclined mixer,
1000 DEG C of calcining 12h in Muffle furnace, air of the atmosphere for 5L/min, material furnace cooling,
400 mesh sieves are crossed after crushing.30mL water is added in agitator tank, after the material after adding 30g to sieve,
Add the Al of certain mass fraction2O3Dispersion liquid 0.11g (ensures that aluminum covering amount is 0.03%), stirs
After mixing 1h, solution is evaporated with vacuum rotary evaporator, is put into 500 DEG C of sintering 8h in high temperature furnace
300 mesh sieves are crossed afterwards, finally give the LiNi that aluminum is evenly coated0.5Co0.2Mn0.3O2, other steps
With embodiment 1.
Embodiment 11-15
Based on pure phase LiNi that embodiment 1 is obtained0.5Co0.2Mn0.3O2, add the oxygen of different quality
Change aluminum dispersion liquid, make the covering amount of final aluminum be respectively 0.1%, 0.5%, 1%, 3%, 5%,
Other steps are with embodiment 10.
Embodiment 16
Nickel sulfate, cobaltous sulfate and manganese sulfate are made into into mixed solution according to Ni：Co：Mn mole
Than for 0.70:0.15:0.15 mix homogeneously, Ni, Co, Mn tri- kinds of transition metal ionss always rub
Your number is 2mol/L, then by the NaOH solution and transition metal ion solution of 4mol/L and
The ammonia of 4mol/L is added in reaction vessel simultaneously, and the pH value for controlling reaction system is 11.8,
Reaction temperature is 60 DEG C.Then, after the precipitation for obtaining filtration, washing, it is dried at 120 DEG C
12 hours.By lithium carbonate and Ni0.7Co0.15Mn0.15(OH)2According to Li/M=1.10 (M=
Ni0.7Co0.15Mn0.15(OH)2) ratio mixed, the mix homogeneously in inclined mixer,
840 DEG C of calcining 12h in Muffle furnace, oxygen of the atmosphere for 10L/min, material furnace cooling,
400 mesh sieves are crossed after crushing.
30g materials after sieving are mixed with 100mL pure water, after constantly stirring 20min, are opened
Beginning squeezes into Al (NO3)3Aqueous solution, the solution prepared as follows：The addition of Al is
The 0.3% of Li-Ni class composite positive poles, after continuing stirring 20min, uses vacuum rotary evaporator
Solution is evaporated, and is put in high temperature furnace and 300 mesh sieves is crossed after 500 DEG C of sintering 8h, finally gives aluminum bag
Cover uniform LiNi0.7Co0.15Mn0.15O2, other steps are with embodiment 1.
Embodiment 17-19
Based on pure phase LiNi that embodiment 16 is obtained0.7Co0.15Mn0.15O2, add different quality
Al(NO3)3Aqueous solution, make final aluminum covering amount be respectively 1%, 3%, 5%, other
Step is with embodiment 1.
Table 1 represents the manufacturing condition of the Li-Ni composite positive poles of the aluminum cladding of above-described embodiment
And its electric performance test result.
For the Li-Ni composite positive poles (embodiment 1) for obtaining, particle surface pattern passes through
Scanning electron microscope is measured, it may be clearly seen that particle surface covers one layer in Fig. 2 right figures
The clad of the aluminium oxide being evenly coated.
For the Li-Ni composite positive poles (embodiment 1) for obtaining, cycle performance passes through Soft Roll
Battery carries out discharge and recharge in 2.75-4.2V and is estimated.As shown in figure 3, material shows well
Cycle performance.
In embodiment, by controlling the test bars such as cladding mode, covering amount and two burning temperature
Part, covers one layer of equally distributed clad in particle surface, and this is greatly improved the peace of battery
Full property and cyclical stability.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate the act made by the present invention
Example, and it is not the restriction to embodiments of the present invention.For the ordinary skill of art
For personnel, the change or change of other multi-forms can also be made on the basis of the above description
It is dynamic.Here all of embodiment cannot be exhaustive.Every technical side for belonging to the present invention
Case it is extended obvious change or change still in protection scope of the present invention row.
Claims (6)
1. the power lithium-ion rechargeable battery composite positive pole of a kind of high safety, its feature exist
In：Chemical formula is LixNiyCozMn1-y-zO2, 0.9<x<1.3,0<y<1,0<z<1, y+z≤1；
The power lithium-ion rechargeable battery composite positive pole be powder, tap density
≥1.5g/cm3。
2. the power lithium-ion rechargeable battery of high safety according to claim 1 is compound just
The preparation method of pole material, it is characterised in that including following step：
(1)NiyCozMn1-y-z(OH)2Preparation：
By soluble nickel salt, cobalt salt and manganese salt according to Ni:Co:Mn=y:z:(1-y-z) rub
, than being made into mixed solution A, the concentration of mixed solution is 0.1～3mol/L for you, and compound concentration is
NaOH solution B of 0.4～10mol/L, concentration are the ammonia spirit C of 2～10mol/L；
Pure water is added in reaction vessel, pH to 9.5～12 is adjusted with NaOH solution and ammonia, by A,
Tri- kinds of solution of B, C are added in reaction vessel simultaneously, and reaction temperature is maintained at 50～80 DEG C,
PH is maintained at 9.5～12, and mixing speed 200-800r/min, the whole process of reaction lead to inertia
Gas shield；The precipitation for obtaining is filtered after terminating by reaction, washing, is dried at 80-200 DEG C
4-8h obtains NiyCozMn1-y-z(OH)2；
(2)LixNiyCozMn1-y-zO2Preparation：
Step (1) is obtained into NiyCozMn1-y-z(OH)2With lithium source Li in molar ratio：M(M
For NiyCozMn1-y-z(OH)2) mixed equal to 0.9～1.2；By the material of mix homogeneously
Sinter in high temperature furnace, sintering temperature is 700-1100 DEG C, sintering time is 10～16h, so
Afterwards cooling, it is broken, crush, screening, except ferrum, obtain LixNiyCozMn1-y-zO2Material；
(3) liquid phase coating aluminum：
Step (2) resulting materials LixNiyCozMn1-y-zO2It is added to the solubility for having dissolved
Feed liquid is obtained in the solution of silicon source, feed temperature is 30～70 DEG C, and solid content is 10～50%,
Gained feed liquid is stirred, is vacuum dried, is then obtained in 400～800 DEG C of 5～10h of constant temperature
To the Li being evenly coatedxNiyCozMn1-y-zO2Material.
3. the power lithium-ion rechargeable battery of high safety according to claim 2 is compound just
The preparation method of pole material, it is characterised in that：The nickel salt, cobalt salt and manganese salt, using sulphuric acid
One or more in salt, chlorate, nitrate, acetate.
4. the power lithium-ion rechargeable battery of high safety according to claim 2 is compound just
The preparation method of pole material, it is characterised in that：The lithium source using lithium carbonate, Lithium hydrate,
One or more in lithium nitrate.
5. the power lithium-ion rechargeable battery of high safety according to claim 2 is compound just
The preparation method of pole material, it is characterised in that：Source of aluminium, using aluminum isopropylate., hydroxyl oxygen
Change one or more in aluminum, aluminum nitrate, aluminum chloride, nano aluminium oxide dispersion liquid, the bag of aluminum
The amount of covering is in 0.03～5wt%.
6. the power lithium-ion rechargeable battery of high safety according to claim 2 is compound just
The preparation method of pole material, it is characterised in that：When step (3) is stirred to gained feed liquid,
Mixing speed is 100～1000r/min, and mixing time is 0.5～4h.
Priority Applications (1)
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| CN109411710A (en) * | 2017-08-17 | 2019-03-01 | 江苏津谊新能源科技有限公司 | A kind of lithium ion battery material and preparation method thereof |
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| CN107706373B (en) * | 2017-09-19 | 2020-05-22 | 合肥国轩高科动力能源有限公司 | High-nickel ternary material for lithium ion battery and preparation method thereof |
| CN107706373A (en) * | 2017-09-19 | 2018-02-16 | 合肥国轩高科动力能源有限公司 | A kind of nickelic ternary material of lithium ion battery and preparation method thereof |
| CN111937194A (en) * | 2018-04-06 | 2020-11-13 | 松下知识产权经营株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN111937194B (en) * | 2018-04-06 | 2023-04-04 | 松下知识产权经营株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN112154558A (en) * | 2018-06-20 | 2020-12-29 | 株式会社Lg化学 | Positive electrode active material for lithium secondary battery and lithium secondary battery |
| CN109346719A (en) * | 2018-11-09 | 2019-02-15 | 浙江德升新能源科技有限公司 | A kind of method that auxiliary agent additive process prepares modified nickel-cobalt lithium manganate cathode material |
| CN109346719B (en) * | 2018-11-09 | 2020-12-01 | 浙江德升新能源科技有限公司 | Method for preparing modified nickel cobalt lithium manganate positive electrode material by aid of additive addition method |
| CN109678217A (en) * | 2018-12-16 | 2019-04-26 | 浙江美都海创锂电科技有限公司 | The Ni of high-tap density0.8Co0.1Mn0.1(OH)2The preparation method and application of material |
| CN109678217B (en) * | 2018-12-16 | 2021-12-31 | 浙江海创锂电科技有限公司 | High tap density Ni0.8Co0.1Mn0.1(OH)2Preparation method and application of material |
| CN113264560A (en) * | 2021-05-17 | 2021-08-17 | 青海师范大学 | Double-coated NCM811 cathode material and preparation method thereof |
| CN115465899A (en) * | 2022-09-14 | 2022-12-13 | 陕西红马科技有限公司 | Multi-crown multi-element spherical coating precursor, preparation method thereof, chemical coating modified product and chemical coating modification method |
| CN115465899B (en) * | 2022-09-14 | 2023-09-15 | 陕西红马科技有限公司 | Multi-crown multi-element spherical coating type precursor, preparation method thereof, chemical coating modified product and chemical coating modified method |
| CN115403080A (en) * | 2022-10-31 | 2022-11-29 | 宜宾锂宝新材料有限公司 | Single crystal type nickel-cobalt-aluminum-lithium oxide positive electrode material and preparation method thereof |
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